Compositions for cleaning organic and plasma etched residues for semiconductor devices

ABSTRACT

A composition for the stripping of photoresist and the cleaning of residues from substrates, and for silicon oxide etch, comprising from about 0.01 percent by weight to about 10 percent by weight of one or more fluoride compounds, from about 10 percent by weight to about 95% by weight of a sulfoxide or sulfone solvent, and from about 20 percent by weight to about 50 percent by weight water. The composition may contain corrosion inhibitors, chelating agents, co-solvents, basic amine compounds, surfactants, acids and bases.

CLAIM OF PRIORITY

This application is a continuation-in-part of U.S. application Ser. No.09/903,064, filed Jul. 10, 2001, now U.S. Pat. No. 6,777,380, whichclaims the benefit of U.S. Provisional Patent Application No.60/217,650, filed Jul. 10, 2000, both of which are incorporated hereinby reference in their entirety.

FIELD OF THE INVENTION

This invention relates to semi-aqueous stripping and cleaningcompositions that are particularly useful for stripping photoresists andcleaning organic and inorganic compounds, including post etch and postash residues, from a semiconductor substrate. The invention is alsouseful as a silicon oxide etchant.

BACKGROUND

Fluoride containing chemistries have been used for many years with primesilicon wafers (wafers that have not yet undergone ion implantation ordevice construction) in the semiconductor industry. Normally thefluoride chemistry (usually dilute hydrofluoric acid) is used as thelast process step in the sequence called “RCA rinses”. The substrate isoften contaminated from previous process steps with monolayer amounts ofmetal, anions and/or organic contaminants or surface residues(particles). These contaminants have been shown to have a significantimpact on the electrical integrity of simple test device structures andthese structures need to be cleaned efficiently without impairing theirintegrity. Such cleaning methods could include techniques discussed inthe technical literature, for example, mt. Conf. On Solid State Devicesand Materials, 1991, pp. 484-486 or Kujime, T. et al., Proc. of the 1996Semi. Pure Water and Chemicals, pp. 245-256 and Singer, P., Semi.International, p. 88, October 1995.

Patents that teach methods for cleaning prime wafers with low pHsolutions include U.S. Pat. Nos. 5,560,857 and 5,645,737; 5,181,985;5,603,849; 5,705,089.

Using fluoride chemistries (usually HF) as a final RCA cleaning stepwill cause the silicon wafer surface to be in a hydrophobic state (thesurface is covered with Si-H groups) which will repel water. During thisstep a certain proportion of the wafer surface is dissolved (removed).Unless the conditions are carefully monitored (time, temperature,solution composition) the substrates can be damaged, as reported byRafols, C. et al., J. Electroanalytic Chem. 433. pp. 77-83, 1997.Numerous compositions combine water and organic solvents. The waterconcentration in these solutions is very critical. Silica oxide has anetch rate of 21 Å/min (@ 25° C.) in HF/water, but in isobutanol the ratewas reduced to 2.14 Å/min and even lower in acetone (an aprotic solvent)the rate was only 0.12 Å/min, as reported at NSF/SRC Eng. Res. Center,Environmentally Benign Semiconductor Manufacturing, Aug. 5-7, 1998,Stanford University.

After the Front End of Line (FEOL) cleaning process the wafer proceedsto the typical Back End of Line (BEOL) manufacturing process forsemiconductor devices, in which the devices might be dynamic randomaccess memories (DRAMs), static random access memories (SRAMs), logic,electrically programmable read only memories (EPROMs), complementarymetal on silicon (CMOS), and the like. Etching fabrication technologyusing chemical reactions (liquid or plasma) has been used as a method offorming a wiring structure on such semiconductor substrates.

A photoresist film is deposited on the wafer to form a mask, then asubstrate design is imaged on the film layer, baked, and the undevelopedimage is removed with a developer. The remaining image is thentransferred to the underlying material through etching (either adielectric or metal) with reactive etching gases promoted with plasmaenergy.

The etchant gases selectively attack the unprotected area of thesubstrate. Liquid or wet etching chemistries have been used extensivelyover the years to etch metals, oxides and dielectrics. These chemistriescan be very aggressive and can result in isotropic etching (etchingequally in all directions).

Increasingly, plasma etching, reactive ion etching or ion milling areused, and such etching processes produce undesirable by-products fromthe interaction of the plasma gases, reacted species and thephotoresist. The composition of such by-products is generally made up ofthe etched substrates, underlying substrate, photoresist and etchinggases. The formation of such by-products is influenced by the type ofetching equipment, process conditions and substrates utilized. Theseby-products are generally referred to as “sidewall polymer,” “veil” or“fences” and cannot be removed completely by either oxygen plasma orconventional solvents. Examples of alkaline/solvent mixture types ofphotoresist strippers which are known for use in stripping applicationsinclude dimethylacetamide or dimethylformamide and alkanolamines asdescribed in U.S. Pat. Nos. 4,770,713 and 4,403,029; 2-pyrrolidone,dialkylsulfone and alkanolamines as described in U.S. Pat. Nos.4,428,871, 4,401,747, and 4,395,479; and 2-pyrrolidone andtetramethylammonium hydroxide as described in U.S. Pat. No. 4,744,834.Such stripping compositions, however, have only proven successful incleaning “sidewall polymer” from the contact openings and metal lineetching in simple microcircuit manufacturing involving a single layer ofmetal process when the metal structure involves mainly Al—Si or Al—Si—Cuand the “sidewall polymer” residue contains only an organometalliccompound with aluminum.

If etching residue is not removed from the substrate, the residue caninterfere with subsequent processes involving the substrate. The need toeffectively remove etching residue and photoresist from a substratebecomes more critical as the industry progresses into submicronprocessing techniques. The requirement for cleaning solutions thatremove all types of residue generated as a result of plasma etching ofvarious types of metals, such as aluminum, aluminum/silicon/copper,titanium, titanium nitride, titanium/tungsten, tungsten, silicon oxide,polysilicon crystal, etc., while not corroding the underlying metalpresents a need for more effective chemistry in the processing area. Theeffect of poor cleaning results in low device yield, low devicereliability, and low device performance.

Also, if the components in these residues are not removed or neutralizedin some manner then the residues will absorb moisture and form acidicspecies that can corrode the metal structures. The resultant acidcorrodes wiring materials to bring about an adverse effect such as anincrease in electrical resistance and wire disconnection. Such problemsfrequently occur, in particular in aluminum and aluminum alloysgenerally used as wiring material. The wafer substrate in contact withacidic materials, if not controlled, can destroy the metal structures.Following completion of the etching operation it is necessary that thepost-etch resist mask be removed from the protective surface to permitfinishing operations.

It is desirable to develop an improved cleaning composition to removethe organic polymeric substance from a coated inorganic substratewithout corroding, dissolving or dulling the metal circuitry orchemically altering the wafer substrate.

Sidewall residues have been removed with either acidic organic solventsor alkaline organic solvents. The acidic solvents are generally composedof phenolic compounds or chloro-solvent and/or an aromatic hydrocarbonand/or alkylbenzenesulfonic acids. These formulations generally need tobe used at temperatures up to and beyond 100° C. These chemistriesnormally need to be rinsed with isopropanol.

In addition, stripping compositions used for removing photoresistcoatings and cleaning compositions for removing post-etch residue havefor the most part been highly flammable, generally hazardous to bothhumans and the environment, and comprise reactive solvent mixturesexhibiting an undesirable degree of toxicity. Moreover, thesecompositions are not only toxic, but their disposal is costly since theymight have to be disposed of as a hazardous waste. In addition, thesecompositions generally have severely limited bath life and, for the mostpart, are not recyclable or reusable.

The photoresist around the contact hole of common interlayerdielectrics, TEOS (tetraethylorthosilicate) and boron phosphosilicateglass (BPSG), which are commonly used in ultra large scale integration(ULSI) structures for better conformity of step coverage, is usuallyremoved with HF solutions. It is not uncommon for the HF to also attackthe dielectric material. Such attack is not desirable (see Lee, C. andLee, S. C., Solid State Electronics, 41, pp. 921-923 (1997)).Accordingly, a need exists for a more environmentally friendly strippingand cleaning formulation.

Dilute hydrofluoric acid solutions can under certain conditions removethe sidewall polymers by aggressively attacking the via sidewall of thedielectric and therefore changing the dimensions of the device, astaught by Ireland, P., Thin Solid Films, 304, pp. 1-12 (1997), andpossibly the dielectric constant. Previous chemistries that contain HF,nitric acid, water and hydroxylamine are aggressive enough to etchsilicon, as taught by U.S. Pat. No. 3,592,773 issued to A. Muller.Recent information also indicates that the dilute HF solutions can beineffective for cleaning the newer CF_(x) etch residues, as taught by K.Ueno et al., “Cleaning of CHF₃ Plasma-Etched SiO₂/SiN/Cu Via Structureswith Dilute Hydrofluoric Acid Solutions,” J. Electrochem. Soc., vol.144, (7) 1997. Contact holes opened on to the TiSi₂ have also beendifficult to clean with HF solutions since there appears to be an attackof the underlying TiSi₂ layer. There may also be difficulty with masstransport of the chemicals in the narrow hydrophilic contact holes, astaught by Baklanov, M. R. et al., Proc. Electrochem. Soc., 1998, 97-35,pp. 602-609.

Recently, fluoride-based chemistries have been used in limited cases toremove post etch residues. Many of these compositions contain fluoridecomponents, specifically hydrogen fluoride. In addition, thesecompositions might contain strong caustic chemicals(choline-derivatives, tetraalkyl ammonium hydroxide, ammonium hydroxide)such as disclosed in U.S. Pat. No. 5,129,955; U.S. Pat. No. 5,563,119;or U.S. Pat. No. 5,571,447, or might use a two-phase solvent system,which contains one phase with hydrofluoric acid and water while a secondphase contains a nonpolar organic solvent (ketones, ethers, alkanes oralkenes) (U.S. Pat. No. 5,603,849). Other formulations includehydroxylamine and ammonium fluoride (U.S. Pat. No. 5,709,756, issued toWard). Additional examples include quaternary ammonium salt and fluoridebased compositions, as disclosed in published European Application0662705, and organocarboxylic ammonium salt or amine carboxylate andfluoride based compositions, as disclosed in U.S. Pat. No. 5,630,904.

Other methods for cleaning metal and metal oxide residues on wafersinclude spraying water vapor into the plasma ashing chamber followed byintroducing fluorine containing gases (hydrofluoric acid) (U.S. Pat. No.5,181,985) or a liquid containing hydrofluoric acid, ammonium fluorideand water with a pH between 1.5 to less than 7.

Some chemistries have also included chelating agents to help removeionic and anionic contamination from the wafer surface (PCT US98/02794)but chelating agents such as citric acid, gallic acid, and catecholamong others, can be aggressive toward the aluminum oxide that coversthe Al metal lines. Studies by Ohman and Sjoberg show that the strongcomplexing ability of citric ions can increase the aluminum oxidesolubility and thereby expose the metal to further corrosion, by factorsof 166 and 468 at pH 5 and 6 (see Ohman et al., J. Chem. Soc., DaltonTrans. (1983), p. 2513).

Other resist-remover chemistries, such as those in U.S. Pat. No.5,792,274, have included a salt of hydrogen fluoride combined with awater-soluble organic solvent and water at a pH of 5 to 8. However, nomention is made of the use of ammonium hydrogen fluoride (also known asammonium bifluoride), which provides greater stability than ammoniumfluoride, or the use of a synergistic mixture of co-solvents or basicamine compounds with DMSO and a fluorinated compound.

U.S. Pat. No. 6,048,406 issued Apr. 11, 2000 to Misra et al. entitled“Benign Method for Etching Silicon Dioxide” teaches using an aqueoussolution of ammonium hydrogen fluoride ((NH₄)HF₂) as an alternative tohydrofluoric acid because it is more benign for wet etching siliconoxide. However, there is no teaching of the use of a formulation thatcan remove photoresist or an etching residue. Also, there is no teachingof adding a synergistic mixture of co-solvents or basic amine compounds.

U.S. Pat. No. 5,885,477 issued Mar. 23, 1999 to Rasmussen et al.entitled “Silicon Dioxide Etch Process Which Protects Metal” teachesusing an aqueous solution of ammonium fluoride and hydrofluoric acidwith a salt to etch silicon oxide while minimizing corrosion. However,there is no teaching of the use of ammonium hydrogen fluoride,co-solvents or basic amine compounds.

U.S. Pat. No. 4,508,591 issued Apr. 2, 1985 to Bartlett et al. entitled“Polymethyl Methacrylate Compatible Silicon Dioxide Complexing Agent”teaches using ammonium fluoride and citric acid to etch silicon dioxide.However, as with Rasmussen et al., there is no teaching of the use ofammonium hydrogen fluoride, co-solvents or basic amine compounds. Nor isthere any teaching to use such a formulation for removing etch residueor photoresist.

Accordingly, there exists a need to develop improved silicon dioxideetchant and photoresist and post-etch residue remover for a variety ofunwanted materials from a wide variety of substrates. Particularly inthe field of integrated circuit fabrication, it should be recognizedthat the demands for improved removal performance with avoidance ofattack on the substrates are constantly increasing. This means thatcompositions that were suitable for less sophisticated integratedcircuit substrates may not be able to produce satisfactory results withsubstrates containing more advanced integrated circuits in the processof fabrication. These compositions should also be economical,environmental friendly and easy to use.

The discussion of the background to the invention herein is included toexplain the context of the invention. This is not to be taken as anadmission that any of the material referred to was published, known, orpart of the common general knowledge as at the priority date of any ofthe claims.

Throughout the description and claims of the specification the word“comprise” and variations thereof, such as “comprising” and “comprises”,is not intended to exclude other additives, components, integers orsteps.

SUMMARY OF THE INVENTION

Accordingly, the present invention teaches a new and improved strippingand cleaning composition and a process for its use. The presentinvention also includes silicon oxide etching compositions and theiruse. This composition is aqueous, dissolves both organic and inorganicsubstances, and, when used in the process, is able to strip and clean avariety of substrates.

The novel stripping, cleaning and etching compositions of the inventionexhibit synergistically enhanced capabilities that are not possible fromthe use of the individual components, or the components in combinationwith other components.

It is one objective of the invention to provide etch residue removingcompositions that: effectively clean post-etch residues from substrates,inhibit redeposition of metal ions, and are corrosion resistant.

It is a further objective of the invention to provide effectivephotoresist stripping compositions.

Another objective is to provide effective silicon oxide etchingcompositions.

These and related objectives are attained through the use of thecomposition and process disclosed herein.

A composition in accordance with this invention is for photoresiststripping and comprises from about 0.01 percent by weight to about 10percent by weight of one or more fluoride compounds, an effective amountof up to about 95 percent by weight of one or more solvents that aresulfoxides or sulfones, and at least about 20 percent by weight water.Additionally, the composition may optionally contain basic amines,co-solvents, corrosion inhibitors, chelating agents, surfactants, acidsand bases. A preferred embodiment contains ammonium hydrogen fluoride,DMSO, and water.

A composition in accordance with this invention is for post-etch residuecleaning and comprises from about 0.01 percent by weight to about 10percent by weight of one or more fluoride compounds, an effective amountof from about 10 to about 95 percent by weight of one or more certainsolvents, and at least about 20 percent by weight water. A preferredembodiment consists of ammonium hydrogen fluoride, DMSO, and water.

Additionally, the composition may optionally contain basic amines,co-solvents, corrosion inhibitors, chelating agents, surfactants, acidsand bases.

Another preferred composition for cleaning and stripping consists ofammonium hydrogen fluoride, DMSO, water, and a co-solvent selected fromthe group consisting of acetic acid, methyl acetate, methyl lactate,ethyl acetate, ethylene glycol diacetate, ethyl lactate, propyleneglycol, propylene carbonate, N-methyl pyrrolidone, glycol ethers such asmethoxyethoxyethanol, butoxyethoxyethanol, and the like, andpolyethylene glycol monolaurate.

Another preferred composition for cleaning and stripping consists ofammonium hydrogen fluoride, DMSO, water, and a basic amine selected fromthe group consisting of hydroxylamine, hydrazine, 2-amino-2-ethoxyethanol, monoethanolamine, diethylhydroxylamine, choline,tetramethylammonium formate, monoisopropanolamine, diethanolamine, andtriethanolamine.

If said composition in accordance with this invention is used for metaland oxide etching, the content of the fluoride compound is elevated. Forexample, for use as a silicon etchant, it is preferred to have about 20%of a 40% aqueous ammonium fluoride solution.

A process for photoresist stripping in accordance with this inventioncomprises contacting the substrate with a composition comprising one ormore fluoride compounds, water and sulfoxide solvent at a temperatureand for a time sufficient to strip the photoresist.

A process for cleaning residue from a substrate in accordance with thisinvention comprises contacting the substrate with a compositioncomprising one or more fluoride compounds, water and sulfoxide solventat a temperature and for a time sufficient to clean the substrate.

A process for metal or oxide etch in accordance with this inventioncomprises contacting the metal or oxide with a composition comprisingone or more fluoride compounds, water and sulfoxide or sulfone solventat a temperature and for a time sufficient to etch the metal or oxide.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an SEM of a via effectively cleaned using a formulationcontaining a co-solvent.

FIG. 2 shows the effect of choline on the etch rate of fluoridecontaining compounds.

FIG. 3 shows the inverse relationship of corrosion rate v. the etch rateof HF₂ ⁻.

FIGS. 4A, 4B and 4C show the results of cleaning with hydrofluoric acid,ammonium hydrogen fluoride and ammonium fluoride respectively.

FIGS. 5A, 5B and 5C show the cleaning results when using differentadditional compounds, propylene glycol, acetyl acetone and2-amino-2-ethoxy ethanol, respectively.

FIGS. 6A and 6B show results of cleaning vias using ester co-solvents.

FIG. 7 shows the results with a 1:1.5:1 ratio of dimethylsulfoxide/ethyllaurate/water.

DETAILED DESCRIPTION

This invention relates to semi-aqueous stripping and cleaningcompositions that are particularly useful for stripping photoresists andcleaning organic and inorganic compounds, including post etch and postash residues, from a semiconductor substrate. The invention is alsouseful as a silicon oxide etchant. As used herein, the term “semiaqueous” refers to a mixture of water and organic solvent. The inventionalso includes methods of using this composition to strip photoresists,clean organic and inorganic compounds from semiconductor substrates, andetch silicon oxide. More particularly, the invention describes semiaqueous stripping, cleaning and etching compositions and processes forthe use thereof. The solutions contain fluoride compounds, sulfoxide orsulfone solvents, water and may contain other solvents, corrosioninhibitors, chelating agents, basic amine compounds, surfactants, acidsand bases.

The manufacture of electronic devices typically involves the use ofphotoresist removers, etch residue removers and silicon oxide etchantsat particular times in the manufacturing process. Fluoride containingformulations have been used to some extent for these purposes. However,some formulations with fluoride containing compounds such as ammoniumfluoride have given inconsistent silicon oxide etch rates due to theevaporation of ammonia from the liquid phase. When the ammonia evolvesfrom the solution, the concentration of the active species of HF₂ ⁻ andHF increases and more aggressively attacks the silicon dioxide. Inaddition, it has been found that the use of aqueous formulations offluoride compounds, such as ammonium fluoride and hydrofluoric acid, andsolvents, such as dimethylsulfoxide, fail to provide adequate resist andresidue removal without significant corrosion of the underlying metalunless additional compounds are added to the formulation.

The present invention discloses novel formulations which provideconsistent silicon oxide etch rates and effectively remove photoresistand etch residues while inhibiting the corrosion of the underlyingmetal. In one embodiment, the present invention applies the use ofaqueous fluoride formulations that use ammonium hydrogen fluoride, whichis a more stable fluoride compound and does not result in the sameproblems experienced by ammonium fluoride and hydrogen fluorideregarding either inconsistent silicon oxide rates or excessivecorrosion.

In another embodiment, the invention applies the use of aqueous fluorideformulations with sulfoxide and sulfone solvents and co-solventsincluding esters such as methyl acetate, ethyl acetate, butyl acetate,methyl lactate, and ethyl lactate, glycols such as propylene glycol,ethylene glycol diacetate, polyethylene clycol monolaurate, lactams suchas N-methyl pyrrolidone and the like, and other suitable solvents suchas propylene carbonate, glycol ethers such as2-(2-methoxyethoxy)ethanol, and 2-(2-butoxyethoxy)ethanol (also known asdiethylene glycol monobutyl ether), and the like, which aid in thecleaning effectiveness of the fluoride formulation.

It is to be understood that the glycol ether co-solvents for use withthe present invention are preferably lower alkyl glycol ethers such asdiethylene glycol ethers, and the alkoxy substituent groups are alsopreferably lower alkyl groups with from 1 to 5 carbon atoms. Such glycolether co-solvents are expressed by the following formula:

In this formula, R is a lower alkyl, with preferably 1 to 5 carbon atomsand may be straight chain or branched. Even more preferably, R is abutyl group. In other embodiments, R may have from 6 to 10 carbon atomsand may be straight chain or branched. The integers m and n are alsopreferably in the range 1 to 5, but may also lie in the range 1 to 10.Even more preferably, m=2 and n=2. Although represented as chains, the(CH₂)_(m) and (CH₂)_(n) groups may also admit to branching.

In another embodiment, the invention applies the use of aqueous fluorideformulations with sulfoxide and sulfone solvents and basic aminecompounds such as 2-amino-2-ethoxy ethanol, monoethanolamine,monoisopropanolamine and the like which assist in cleaning effectivenessand inhibit corrosion.

These embodiments can be used separately or combined.

The first component of the compositions of the present invention is afluoride containing compound which may be used alone or in combinationwith at least one other fluoride containing compound. The fluoridecontaining compound or mixture of compounds is suitably selectedaccording to the situation and is in the range of about 0.01 percent byweight to about 10 percent by weight.

Suitable fluoride compounds are ammonium fluoride, ammonium hydrogenfluoride and hydrogen fluoride. The preferred fluoride compounds areammonium fluoride and ammonium hydrogen fluoride. The most preferredfluoride compound is ammonium hydrogen fluoride. For removing residuesand photoresists, the fluoride compounds are desirably present in anamount of from about 0.01 percent by weight to about 10 weight percent.In general, the lower the concentration of the fluoride compound in thecomposition, the higher the temperature of use needs to be.

The silicon oxide etch compositions of the present invention alsocontain one or more fluoride compounds but the compounds are preferablypresent in an amount from about 7 weight percent to about 10 weightpercent.

The second component include sulfoxide solvents and sulfone solvents ormixtures thereof which correspond to the following:

where R₁ and R₂ are an H, OH or alkyl group, and at least one is analkyl group, and

where R₃-R₁₀ are independently H or an alkyl group.

Suitable sulfoxide solvents include the following and mixtures thereof:dimethyl sulfoxide (DMSO), dipropylsulfoxide, diethylsulfoxide,methylethylsulfoxide, diphenylsulfoxide, methylphenylsulfoxide,1,1′-dihydroxyphenyl sulfoxide and the like.

Suitable sulfone solvents include the following and mixtures thereofdimethylsulfone, diethylsulfone, and the like. The sulfoxide or sulfonesolvents or mixtures thereof are suitably selected according to thesituation and are present in the range of about 10 percent by weight toabout 95 percent by weight.

A preferred embodiment has a solvent to water ratio of about 60:40although higher or lower ratios may be suitable depending on theparticular application. At a ratio of about 60:40 solvent to water noover etching was observed and all residues were removed. Significantlyhigher solvent to water ratios may lead to over etch of the viasidewall.

As stated earlier, aqueous formulations using a fluoride containingcompound that is not ammonium hydrogen fluoride with a sulfoxide solventwill not provide adequate cleaning without resulting in significantcorrosion. Thus, where ammonium hydrogen fluoride is not used, one ormore co-solvents or basic amine compounds are added to optimize theeffectiveness of the formulation while minimizing corrosion. Suitableco-solvents include the following and mixtures thereof: N-alkyl lactams,such as N-methyl-2-pyrrolidone, ester compounds such as acetic acid,methyl acetate, methyl lactate, ethyl acetate, ethyl lactate, glycolssuch as propylene glycol, ethylene glycol diacetate, polyethylene glycolmonolaurate and other suitable co-solvents such as propylene carbonate,methoxyethoxyethanol, butoxyethoxyethanol, and the like.

Suitable basic amine compounds include the following and mixturesthereof: hydroxylamine, hydrazine, 2-amino-2-ethoxy ethanol (DGA),monoethanolamine (MEA), diethylhydroxylamine, cholines,tetramethylammonium formate (TMAF), monoisopropanolamine (MIPA),diethanolamine (DEA), triethanolamine (TEA) and the like.

It has been found that the use of ammonium hydrogen fluoride, orammonium bifluoride, provides for improved stability over other fluoridecompounds and provides a significantly higher etch rate because itgenerates HF₂ ⁻ directly. Interestingly, HF₂ ⁻ is also the species leastcorrosive to metals. Thus, it has been found that the use of ammoniumhydrogen fluoride will minimize the corrosion of metals as compared toother fluoride compounds.

In addition to the components listed above, the composition containswater. Typically high-purity deionized water is used.

The composition may optionally contain other solvents that would beknown to one skilled in the art, including amides and polyols.

The composition may optionally contain corrosion inhibitors. Suitablecorrosion inhibitors include inorganic nitrate salts such as ammonium,potassium, sodium and rubidium nitrate salts, aluminum nitrate and zincnitrate.

The composition may optionally contain chelating agents. Suitablechelating agents are described in commonly assigned U.S. Pat. No.5,672,577, issued Sep. 30, 1997 to Lee, which is incorporated herein byreference. The addition of a chelator further improves the effectivenessof the formulation used as a etch residue or photoresist remover.

The composition may optionally contain surfactants. Suitable surfactantsinclude poly(vinyl alcohol), poly(ethyleneimine) and any of thesurfactant compositions classified as anionic, cationic, nonionic,amphoteric, and silicone based. Preferred surfactants are poly(vinylalcohol) and poly(ethyleneimine).

Some combinations of components require the addition of acids and/orbases to adjust the pH to an acceptable value. The acids suitable foruse in the present invention are organic or inorganic. The acids caninclude nitric, sulfuric, phosphoric, hydrochloric acids (thoughhydrochloric acid can be corrosive to metals) and the organic acids,formic, acetic, propionic, n-butyric, isobutyric, benzoic, ascorbic,gluconic, malic, malonic, oxalic, succinic, tartaric, citric, andgallic.

The caustic components suitable for use to adjust the pH of the cleaningsolution can be composed of any common base, i.e. sodium, potassium,magnesium hydroxides, or the like. The major problem is that these basesintroduce mobile ions into the final formulation. Mobile ions coulddestroy computer chips being produced today in the semiconductorindustry. Other bases can be used that include ammonium hydroxide orderivatives thereof including trimethyl-2-hydroxyethyl ammoniumhydroxide (choline), and the like.

The method of cleaning a substrate using the cleaning compositions ofthe present invention involves contacting a substrate having residuethereon, particularly organometallic or metal oxide residue, with acleaning composition of the present invention for a time and at atemperature sufficient to remove the residue. Stirring, agitation,circulation, sonication or other techniques as are known in the artoptionally may be used. The substrate is generally immersed in thecleaning composition. The time and temperature are determined based onthe particular material being removed from a substrate. Generally, thetemperature is in the range of from about ambient or room temperature toabout 100° C., preferably 55° C., and the contact time is from about 1to 60 minutes, preferably 5-30 minutes. Generally the substrate will berinsed after using the composition. Preferred rinse solutions areisopropanol and DI water.

The compositions of the invention are particularly useful for removingresidue from metal and via features but are also useful for strippingphotoresists. The application of the present compositions as aphotoresist stripper are easily determined by one of skill in the art.Similarly, the compositions of the present invention are also useful formetal or oxide etch. Such an application and the conditions therefor isalso easily determined by one of skill in the art.

In addition to the benefits of using ammonium hydrogen fluoride, asdescribed above, it has been found that the addition of a basic aminecompound, such as 2-amino-2-ethoxy ethanol and the like, to a aqueousformulation containing a fluoride compound and an organic sulfoxideand/or sulfone solvent effectively neutralizes the HF by forming aquaternary ammonium fluoride salt, for example, according to thefollowing reactions:RNH₂+H₂O−>RNH₃ ⁺+OH⁻HF+OH⁻−>F⁻+H₂ORNH₂+HF−>RNH₃ ⁻+F⁻

Since the F⁻ ions do not attack silicon dioxide, the formulation is lessaggressive and reduces unwanted etching.

It has also been found that by adding a co-solvent, such as ethyllactate and the like, to a aqueous formulation containing a fluoridecompound and an organic sulfoxide and/or sulfone solvent improves thecapability of the formulation to remove etch residues and photoresists.The effect of ethyl lactate on removing etch residues is due to amodification of the hydrophobicity/hydrophilicity balance, wettingability and/or the change of polarity of the blend. The addition of aco-solvent such as ethyl lactate and the like provides for activechemical attack by fluoride species, solvation and dissolution.

The foregoing description is intended to illustrate various aspects ofthe present invention. It is not intended that the examples presentedherein limit the scope of the present invention. The invention now beingfully described, it will be apparent to one of ordinary skill in the artthat many changes and modifications can be made thereto withoutdeparting from the spirit or scope of the appended claims.

EXAMPLES Example 1

A group of cleaning chemistries containing the ingredients of ammoniumfluoride, water, and a sulfoxide or sulfone solvent were tested withmetal wafers which have stacks of TiN/AlCu/TiN/Ti/Oxide etched with achlorinated plasma in a commercially available etcher. The resultingmetal wafers with residues were cut into small sample pieces, and thenthe sample pieces were immersed into the chemistry solutions in Table 1for cleaning for 5 minutes at room temperature. The sample pieces weretaken out, rinsed with deionized water and dried with the flow of N₂.SEM was performed with a Hitachi 4500 FE-SEM for evaluating cleaning andcorrosion effects. Residue removal and corrosion effects on metal stackwere assessed by visual comparisons and were all ranked on a scale of 1to 10. The formulations in table 1 are shown in weight percent. TABLE 1For- 40% DI Time Results mula NH₄F water DMSO ACN HDA (Min.) CleanCorrosion A* 0.75 20 75 0 0 5 10 10 B 1 35 0 64 0 5 10 8 C 1 35 0 0 64 58 10*Formula A also contained 4.25% DMP

In Table 1, the reaction temperature was Room Temperature. DI water isDeionized water; DMSO is Dimethylsulfoxide; ACN is Acetonitrile; and HADis Hydroxylamine. Clean lines are rated on a scale where 1 is poor, and10 is complete. Corrosion is rated on a scale where 1 is a severeattack, and 10 represents no corrosion. The results showed that the DMSOcontaining formulation gave the combination of the best cleaningperformance with the smallest extent of corrosion, in the form of aslight attack on aluminum. On this basis, DMSO was chosen for furtherstudy to provide an enhanced formulation.

Example 2

A blend of 42.6 percent by weight ethyl lactate, 28.4 percent by weightDMSO, 28.4 percent by weight water and 0.4 percent by weight ammoniumhydrogen fluoride was prepared to clean etch residue from a substrate.FIG. 1 shows the effective removal of the etch residue.

Example 3

Ammonium hydrogen fluoride (ammonium bifluoride) was substituted inplace of ammonium fluoride and hydrofluoric acid. As can be seen inFIGS. 4A-4C, the best results were using ammonium hydrogen fluoridewhich effectively removed etch residue without over etching the viabeing cleaned.

Example 4

A investigation of the intrinsic cleaning performance by the differentfunctional groups was undertaken. Propylene glycol was used as ahydroxyl source, acetyl acetone as carbonyl source, and DGA as nitrogensource. The SEM shown as FIGS. 5A-5C indicate that hydroxyl groups mighthelp the removal of the bottom residues while carbonyl might aid thecleaning of the residue on the side-wall of the trench.

Mixing these components, it was found that the two beneficial effects(alcohol and ketone) on the cleaning were conserved within the mixture.This new finding led to the investigation of the residue and photoresistremoval ability of ester groups, which constitute the intermediaryfunctional group in term of polarizability between carboxylicacid/glycol and ketone. The first ester compound tested was methylacetate and gave beneficial results. The benefits of using an estergroup were further confirmed by testing ethylene glycol diacetate andethyl lactate as is shown in FIGS. 6A and 6B. Due to its highersolubility in an aqueous solution, ethyl lactate is the preferred esterand the preferred co-solvent.

Different solutions were made up with different DMSO/ESTER/DIW ratiosand it was found that the preferred ratio is about 1/1.5/1, in the caseof ethyl lactate, as can be seen by the results of SEM FIG. 7.

Based on the results of Example 1, formulations with a variety ofconcentrations of DMSO were tested to determine the effective ranges incombination with ammonium fluoride in the presence of water. The resultsshowed that for cleaning etch resist, DMSO is effective at aconcentrations from about 10 percent by weight to about 95% by weightand the effectiveness of the formulation was enhanced by the addition ofa basic organic amine or a co-solvent. The following table demonstratesformulations found to be more effective and versatile than formulationswith DMSO alone. TABLE 2 Basic Organic Chelating Potential field ofFormula DMSO Co-Solvent Water Fluoride Amine Agents application 1 65.530.6 AF = 1.4 DGA = 2.5 Stable etchant; residue remover, photoresistremover 2 69 29.5 AHF = 1.5 Stable etchant; residue remover, photoresistremover 3 69 27.4 AHF = 1.5 Choline (45% Stable etchant; in water) = 2.1residue remover, photoresist remover 4 69 26 AHF = 1.5 Choline (45%Stable etchant; in water) = 3.5 residue remover, photoresist remover 569 24.6 AHF = 1.5 Choline (45% Stable etchant; in water) = 4.9 residueremover, photoresist remover 6 69 21.8 AHF = 1.5 Choline (45% Stableetchant; in water) = 7.7 residue remover, photoresist remover 7 69 23.120% aq MEA = 0.5 Stable etchant; AHF = 7.4 residue remover, photoresistremover 8 69 22.8 20% aq MEA = 0.8 Stable etchant; AHF = 7.4 residueremover, photoresist remover 9 69 22.5 20% aq MEA = 1.1 Stable etchant;AHF = 7.4 residue remover, photoresist remover 10 69 22 20% aq MEA =1.60 Stable etchant; AHF = 7.4 residue remover, photoresist remover 1169 30 HF = 0.5 MEA = 0.5 Stable etchant; residue remover, photoresistremover 12 69 29.7 HF = 0.5 MEA = 0.8 Stable etchant; residue remover,photoresist remover 13 69 29.4 HF = 0.5 MEA = 1.1 Stable etchant;residue remover, photoresist remover 14 69 28.7 HF = 0.5 MEA = 1.8Stable etchant; residue remover, photoresist remover 15 69 29.7 HF = 0.5DGA = 0.84 Stable etchant; residue remover, photoresist remover 16 6929.1 HF = 0.5 DGA = 1.36 Stable etchant; residue remover, photoresistremover 17 69 28.3 HF = 0.5 DGA = 2.20 Stable etchant; residue remover,photoresist remover 18 69 27.4 HF = 0.5 DGA = 3.15 Stable etchant;residue remover, photoresist remover 19 69 29.3 AF = 0.6; AH Stableetchant; F = 1.1 residue remover, photoresist remover 20 69 29.1 AF =1.2; Stable etchant; AHF = 0.75 residue remover, photoresist remover 2169 28.8 AF = 1.8; Stable etchant; AHF = 0.37 residue remover,photoresist remover 22 69 25.1 AHF Choline (45% Stable etchant; (20% inin water) = 0 residue remover, water) = 5.9 photoresist remover 23 69 23AHF Choline (45% Stable etchant; (20% in in water) = 2.1 residueremover, water) = 5.9 photoresist remover 24 69 21.6 AHF Choline (45%Stable etchant; (20% in in water) = 3.5 residue remover, water) = 5.9photoresist remover 25 69 20.2 AHF Choline (45% Stable etchant; (20% inin water) = 4.9 residue remover, water) = 5.9 photoresist remover 26 6917.4 AHF Choline (45% Stable etchant; (20% in in water) = 7.7 residueremover, water) = 5.9 photoresist remover 27 69 25.5 AHF Stable etchant;(20% in residue remover, water) = 5.5 photoresist remover 28 69 27.3 AHFStable etchant; (20% in residue remover, water) = 3.7 photoresistremover 29 69 27.7 AHF Stable etchant; (20% in residue remover, water) =2.3 photoresist remover 30 10 82.6 AHF Stable etchant; (20% in residueremover water) = 7.4 31 30 62.6 AHF Stable etchant; (20% in residueremover water) = 7.4 32 50 42.6 AHF Stable etchant; (20% in residueremover, water) = 7.4 photoresist remover 33 70 22.6 AHF Stable etchant;(20% in residue remover, water) = 7.4 photoresist remover 34 90 2.6 AHFStable etchant; (20% in residue remover, water) = 7.4 photoresistremover 35 69 28.5 HF(40% aq) = 0.65 Choline = 1.9 Stable etchant;residue remover, photoresist remover 36 69 27.7 HF(40% aq) = 0.65Choline = 2.7 Stable etchant; residue remover, photoresist remover 37 6926.9 HF(40% aq) = 0.65 Choline = 3.5 Stable etchant; residue remover,photoresist remover 38 69 29.6 HF(40% aq) = 0.65 DGA = 0.74 Stableetchant; residue remover, photoresist remover 39 69 29.4 HF(40% aq) =0.65 DGA = 1.0 Stable etchant; residue remover, photoresist remover 4069 29 HF(40% aq) = 0.65 DGA = 1.4 Stable etchant; residue remover,photoresist remover 41 69 25.3 AHF (20% Stable etchant; aq) = 5.7residue remover, photoresist remover 42 69 28.2 AHF (20% Stable etchant;aq) = 2.85 residue remover, photoresist remover 43 69 30.4 AHF (20%Stable etchant; aq) = 0.57 residue remover, photoresist remover 44 8512.2 AHF (20% Stable etchant; aq) = 2.85 residue remover, photoresistremover 45 50 AHF = 3.705 DGA = 50 Stable etchant; residue remover,photoresist remover 46 50 AHF = 1.8525 DGA = 50 Stable etchant; residueremover, photoresist remover 47 69 29.5 AHF (20% MEA = 0.15 Stableetchant; aq) = 1.4 residue remover, photoresist remover 48 69 27.9 AHF(20% MEA = 0.30 Stable etchant; aq) = 2.80 residue remover, photoresistremover 49 69 29.4 AHF (20% MEA = 0.21 Stable etchant; aq) = 1.4 residueremover, photoresist remover 50 69 27.8 AHF (20% MEA = 0.42 Stableetchant; aq) = 2.80 residue remover, photoresist remover 51 69 29.3 AHF(20% MEA = 0.30 Stable etchant; aq) = 1.4 residue remover, photoresistremover 52 69 27.6 AHF (20% MEA = 0.60 Stable etchant; aq) = 2.80residue remover, photoresist remover 53 67.3 28.7 AF = 1.3 DGA = 0.1Gallic Acid = 1.6 Stable etchant; residue remover, photoresist remover54 68.3 Acetic Acid = 0.9 29.5 AF = 1.3 Stable etchant; residue remover,photoresist remover 55 68 Acetic Acid = 0.6 29.2 AF = 2.2 Stableetchant; residue remover, photoresist remover 56 67.9 Acetic Acid = .629.1 AF = 2.2 DGA = 0.1 Stable etchant; residue remover, photoresistremover 57 49.1 NMP = 19.6 29.6 AHF = 1.3 MEA = 0.3 Stable etchant;residue remover 58 19.6 NMP = 49.1 29.5 AHF = 1.3 MEA = 0.3 Stableetchant; residue remover 59 58.3 Ethyl 25 AHF = 0.4 Stable etchant;Acetate = 16.6 residue remover, photoresist remover 60 53.8 Ethyl 23 AHF= 0.4 Stable etchant; Acetate = 15.3; residue remover, PG = 7.7photoresist remover 61 49.7 Ethyl 21 AHF = 0.4 Stable etchant; Acetate =28.4 residue remover 62 46.6 Ethyl 20 AHF = 0.4 Stable etchant; Acetate= 26.6 residue remover PG = 6.6 63 44.9 Ethyl 19.3 AHF = 0.4 Stableetchant; Acetate = 25.8%; residue remover PG = 6.4; Acetyl Acetone = 364 45.5 Ethyl 19.5 AHF = 0.4 Stable etchant; Acetate = 26 residueremover PG = 8.6 65 28.4 Methyl-s- 28.4 AHF = 0.4 Stable etchant;lactate = 42.6 residue remover 66 28.4 Ethyl-s- 28.4 AHF = 0.4 Stableetchant; lactate = 42.6 residue remover 67 24.9 Ethylene glycol 37.3 AHF= 0.4 Stable etchant; diacetate = 37.3 residue remover 68 24.9 Polyethylene 37.3 AHF = 0.4 Stable etchant; glycol mono- residue removerlaurate = 37.3 69 33.1 Ethylene glycol 16.5 AHF = 0.4 Stable etchant;diacetate = 49.7 residue remover 70 28.4 Ethylene glycol 28.4 AHF = 0.4Stable etchant; diacetate = 42.6 residue remover 71 24.9 Ethylene glycol37.3 AHF = 0.4 Stable etchant; diacetate = 37.30 residue remover 72 16.5Ethylene glycol 16.5 AHF = 0.4 Stable etchant; diacetate = 56.8 residueremover 73 14.2 Ethylene glycol 28.4 AHF = 0.4 Stable etchant; diacetate= 52 residue remover 74 12.5 Ethylene glycol 37.4 AHF = 0.4 Stableetchant; diacetate = 49.7 residue remover 75 33.1 Ethyl-s- 16.5 AHF =0.4 Stable etchant; lactate = 49.7 residue remover 76 28.4 Ethyl-s- 28.4AHF = 0.4 Stable etchant; lactate = 42.6 residue remover 77 24.9Ethyl-s- 37.3 AHF = 0.4 Stable etchant; lactate = 37.3 residue remover78 16.5 Ethyl-s- 16.5 AHF = 0.4 Stable etchant; lactate = 56.8 residueremover 79 14.2 Ethyl-s- 28.4 AHF = 0.4 Stable etchant; lactate = 52residue remover 80 12.5 Ethyl-s- 37.4 AHF = 0.4 Stable etchant; lactate= 49.7 residue remover 81 18 NMP = 49 29.3 AF (40%) = 0.75 DGA = 3Residue remover 82 25 NMP = 20; 29.3 AF (40%) = 0.75 Residue remover PC= 25 83 25 PC = 45 29.3 AF (40%) = 0.75 Residue remover 84 25 NMP = 4529.3 AF (40%) = 0.75 Residue remover 85 40 NMP = 30 29.3 AF(40%) = 0.75Residue remover 86 57.25 29.3 AF(40%) = 3.5 DGA = 10 Residue remover 8762.25 29.3 AF(40%) = 3.5 DGA = 5 Residue remover 88 64.25 29.3 AF(40%) =3.5 DGA = 3 Residue remover 89 64.75 29.3 AF(40%) = 3.5 DGA = 2.5Residue remover 90 30 NMP = 36.5; 30 HF(50%) = 0.1 MIPA = 0.5 Residueremover PG = 2.9 91 30 NMP = 34.5; 30 HF(50%) = 0.1 DGA = 2.5 Residueremover PG = 2.9 92 30 NMP = 36.9; 30 HF(50%) = 0.1 MEA = 0.1 Residueremover PG = 2.9 93 30 NMP = 55.5; 10 HF(50%) = 0.1 MEA = 1 DCH = 0.5Residue remover PG = 2.9 94 32 NMP = 52.5; 10 HF(50%) = 0.1 MEA = 2 DCH= 0.5 Residue remover PG = 2.9 95 33.5 NMP = 30; 30 HF(50%) = 0.1 DGA =3.5 Residue remover PG = 2.9 96 34.5 NMP = 55.5; 5 HF(50%) = 0.1 DGA = 2Residue remover PG = 2.9 97 35 NMP = 30; 30 HF(50%) = 0.1 DGA = 2Residue remover PG = 2.9 98 35 NMP = 50; 10 HF(50%) = 0.1 DGA = 2Residue remover PG = 2.9 99 35 NMP = 56.9; 5 HF(50%) = 0.1 MEA = 0.1Residue remover PG = 2.9 100 35.5 NMP = 30; 30 HF(50%) = 0.1 MIPA = 1.5Residue remover PG = 2.9 101 36 NMP = 30; 30 HF(50%) = 0.1 MIPA = 1Residue remover PG = 2.9 102 36 NMP = 30; 30 HF(50%) = 0.1 MEA = 1Residue remover PG = 2.9 103 36.5 NMP = 30; 30 HF(50%) = 0.1 MEA = 0.5Residue remover PG = 2.9 104 36.9 NMP = 30; 30 HF(50%) = 0.1 MIPA = 0.1Residue remover PG = 2.9 105 36.9 NMP = 30; 30 HF(50%) = 0.1 MEA = 0.1Residue remover PG = 2.9 106 37 NMP = 49.9; 10 HF(50%) = 0.1 MEA = 0.1Residue remover PG = 2.9 107 37 NMP = 49.5; 10 HF(50%) = 0.1 MEA = 0.5Residue remover PG = 2.9 108 37 NMP = 54.5; 5 HF(50%) = 0.1 MEA = 0.5Residue remover PG = 2.9 109 37 NMP = 49; 10 HF(50%) = 0.1 MEA = 0.5 DCH= 0.5 Residue remover PG = 2.9 110 37 NMP = 48; 10 HF(50%) = 0.1 MEA =1.5 DCH = 0.5 Residue remover PG = 2.9 111 53.75 PG = 15 27.3 AF(40%) =2.5 HDA ® = 1.5 Residue remover 112 68 28.5 AF(40%) = 2.5 DEHA = 1Residue remover 113 68.5 28.5 AF(40%) = 2.5 DEHA = 0.5 Residue remover114 68.9 28.5 AF(40%) = 2.5 DEHA = 0.1 Residue remover 115 71.8 28HF(50%) = 0.1 TBPH = 0.1 Residue removerwhere:HF = hydrogen fluorideDCH = dicarbethoxy hydrazineAHF = ammonium hydrogen fluoride (ammonium bifluoride)AF = ammonium fluorideMEA = monoethanolaminePG = propylene glycolHDA ® = hydroxylamineMIPA = monoisopropanolamineTBPH = tetrabutyl phosphonium hydroxideTMAF = tetramethylammonium formateDGA = diglycolamineNMP = N-methyl pyrrolidonePC = propylene carbonateDEHA = diethylhydroxylamine

A preferred embodiment comprises: 65.5% DMSO, 3.5% ammonium fluoride(40% aqueous), 28.5% DI water, and 2.5% DGA. (Performance: Clean=10,Corrosion=10).

Another preferred embodiment comprises: 25% DMSO, 0.75% ammoniumfluoride (40% aqueous), 29.25% DI water, and 45% NMP. (Performance:Clean=10, Corrosion=10).

Another preferred embodiment comprises: 40% DMSO, 0.75% ammoniumfluoride (40% aqueous), 29.25% DI water, and 30% NMP. (Performance:Clean=10, Corrosion=10).

Another preferred embodiment comprises: 18% DMSO, 0.75% ammoniumfluoride (40% aqueous), 29.25% DI water, 49.5% NMP, and 3% DGA(Performance: Clean=9.8, Corrosion=10).

The embodiments herein are given by way of example and are not intendedto limit the present invention. One skilled in the art will recognizefrom the foregoing examples that modifications and variations can, andare expected to be made, to the foregoing compositions in accordancewith varying conditions inherent in the production process.

Additionally, with routine experimentation, one skilled in the art caneasily determine effective amounts of each component of the presentinvention for the particular photoresist stripping, post-etch residuecleaning, or metal or oxide etch application.

All publications and patent applications mentioned in this specificationare herein incorporated by reference to the same extent as if eachindividual publication or patent application was specifically andindividually indicated to be incorporated by reference.

The invention now being fully described, it will be apparent to one ofordinary skill in the art that many changes and modifications can bemade thereto without departing from the spirit or scope of the appendedclaims.

1. A composition for stripping photoresist and cleaning etch residuefrom substrates comprising from about 0.01 percent by weight to about 10percent by weight of one or more fluoride compounds, from about 15percent by weight to about 50 percent by weight water, from about 10percent by weight to about 95 percent by weight of a compound which iseither an organic sulfoxide corresponding to the following:

where R₁ and R₂ are H, OH or an alkyl, at least one of R₁ and R₂ is analkyl, or a sulfone solvent corresponding to the following:

where R₃-R₁₀ are independently H or an alkyl group, and and from about0.1 to about 15 percent by weight of a basic amine compound.
 2. Thecomposition of claim 1 wherein said fluoride compound is ammoniumbifluoride and said organic sulfoxide is dimethylsulfoxide.
 3. Thecomposition of claim 1 wherein said fluoride compound is ammoniumfluoride and said organic sulfoxide is dimethylsulfoxide.
 4. Thecomposition of claim 3 wherein said composition comprises about 3.5% byweight of a 40% aqueous solution of ammonium fluoride, about 65.5% byweight dimethylsulfoxide, about 28.5% water, and about 2.5% 2-amino2-ethoxyethanol.
 5. The composition of claim 3 wherein said basic aminecompound is selected from the group consisting of hydroxylamine,hydrazine, 2-amino-2-ethoxy ethanol, monoethanolamine,diethylhydroxylamine, choline, tetramethylammonium formate,monoisopropanolamine, diethanolamine, triethanolamine.
 6. Thecomposition of claim 5 wherein said basic amine compound is choline. 7.The composition of claim 1 wherein the ratio of total solvent/amine towater is from about 1.5:1 to about 2.5:1.
 8. The composition of claim 1wherein said composition comprises about 3.5% by weight of ammoniumfluoride, about 65.5% by weight dimethylsulfoxide, about 28.5% water,and about 2.5% 2-amino 2-ethoxyethanol.
 9. The composition of claim 1further comprising a chelating agent selected from the group consistingof gallic acid, catechol tetrabutyl phosphonium hydroxide anddicarbethoxyhydrazine.
 10. The composition of claim 1 further comprisinga co-solvent.
 11. The composition of claim 10 wherein the co-solvent ispresent in an amount from about 0.1 to about 60 percent by weight. 12.The composition of claim 10 wherein the co-solvent is selected from thegroup consisting of: acetic acid, methyl acetate, methyl lactate, ethylacetate, ethylene glycol diacetate, ethyl lactate, propylene glycol,propylene carbonate, N-methyl pyrrolidone, methoxyethoxyethanol,butoxyethoxyethanol, and polyethylene glycol monolaurate.
 13. A methodof removing a photoresist coating from a substrate using the compositionof any one of claims 1-12.
 14. A method of removing etch residue from asubstrate using the composition of any one of claims 1-12.
 15. Acomposition for stripping photoresist and cleaning etch residue fromsubstrates comprising from about 0.01 percent by weight to about 10percent by weight of one or more fluoride compounds, from about 15percent by weight to about 50 percent by weight water, from about 10percent by weight to about 95 percent by weight of a compound which iseither an organic sulfoxide corresponding to the following:

where R₁ and R₂ are H, OH or an alkyl, at least one of R₁ and R₂ is analkyl, or a sulfone solvent corresponding to the following:

where R₃-R₁₀ are independently H or an alkyl group, and a co-solvent.16. The composition of claim 15 wherein the co-solvent is present in anamount from about 0.1 to about 60 percent by weight.
 17. The compositionof claim 16 wherein the co-solvent is selected from acetic acid, methylacetate, methyl lactate, ethyl acetate, ethylene glycol diacetate, ethyllactate, propylene glycol, propylene carbonate, N-methyl pyrrolidone,methoxyethoxyethanol, butoxyethoxyethanol, and polyethylene glycolmonolaurate.
 18. The composition of claim 17 wherein said fluoridecompound is ammonium hydrogen fluoride and said organic sulfoxide isdimethylsulfoxide.
 19. The composition of claim 17 wherein said fluoridecompound is ammonium fluoride and said organic sulfoxide isdimethylsulfoxide.
 20. The composition of claim 15 further comprising achelating agent selected from the group consisting of gallic acid,catechol, tetrabutyl phosphonium hydroxide and dicarbethoxyhydrazine.21. A method of removing a photoresist coating from a substrate usingthe composition of any one of claims 15-20.
 22. A method of removingetch residue from a substrate using the composition of any one of claims15-20.
 23. A composition for stripping photoresist and cleaning etchresidue from substrates comprising from about 0.01 percent by weight toabout 10 percent by weight of ammonium hydrogen fluoride, from about 15percent by weight to about 50 percent by weight water and from about 10percent by weight to about 95 percent by weight of a compound which iseither an organic sulfoxide solvent corresponding to the following:

where R₁ and R₂ are H, OH or an alkyl, at least one of R₁ and R₂ is analkyl or sulfone solvent corresponding to the following:

where R₃-R₁₀ are independently H or an alkyl group.
 24. The compositionof claim 23 wherein the organic sulfoxide is dimethylsulfoxide.
 25. Thecomposition of claim 24 wherein the composition further contains aco-solvent.
 26. The composition of claim 25 wherein the co-solvent isselected from the group consisting of: acetic acid, methyl acetate,methyl lactate, ethyl acetate, ethylene glycol diacetate, ethyl lactate,propylene glycol, propylene carbonate, N-methyl pyrrolidone,methoxyethoxyethanol, butoxyethoxyethanol, and polyethylene glycolmonolaurate.
 27. The composition of claim 26 wherein said co-solvent isethyl lactate and is present in an amount from about 30 percent byweight to about 60 percent by weight.
 28. The composition of claim 23wherein the composition further contains a basic amine compound selectedfrom the group consisting of hydroxylamine, hydrazine, 2-amino-2-ethoxyethanol, monoethanolamine, diethylhydroxylamine, choline,tetramethylammonium formate, monoisopropanolamine, diethanolamine, andtriethanolamine.
 29. The composition of claim 23 further comprising achelating agent selected from the group consisting of gallic acid,catechol, tetrabutyl phosphonium hydroxide and dicarbethoxyhydrazine.30. A method of removing a photoresist coating from a substrate usingthe composition of any one of claims 23-29.
 31. A method of removingetch residue from a substrate using the composition of any one of claims23-29.
 32. A composition for etching metal or oxide comprising fromabout 7.5 percent by weight to about 10 percent by weight of one or morefluoride compounds, from about 15 percent by weight to about 50% byweight water, and from about 10 percent by weight to about 95% by weightof an organic sulfoxide or sulfone solvent.
 33. A composition foretching silicon oxide comprising: from about 20 percent by weight toabout 40 percent by weight of one or more fluoride compounds, from about15 percent by weight to about 50 percent by weight water, from about 10percent by weight to about 95 percent by weight of a compound which iseither an organic sulfoxide corresponding to the following:

where R₁ and R₂ are H, OH or an alkyl, at least one of R₁ and R₂ is analkyl, or a sulfone solvent corresponding to the following:

where R₃-R₁₀ are independently H or an alkyl group.
 34. The compositionof claim 34 additionally comprising from about 0.1 to about 15 percentby weight of a basic amine compound.
 35. The composition of claim 34wherein the one or more fluoride compounds is selected from the groupconsisting of: ammonium fluoride and ammonium bifluoride.
 36. Thecomposition of claim 35 wherein said fluoride compound is ammoniumbifluoride.
 37. The composition of claim 35 wherein said fluoridecompound is ammonium fluoride.
 38. The composition of claim 34additionally comprising a co-solvent.
 39. A method of etching siliconoxide using the composition of any one of claims 34-39.